Dioxide slime control composition and its use

ABSTRACT

The present invention relates to certain processes and compositions useful for inhibiting and/or controlling the growth of slime in water and, in particular, water employed for industrial purposes. Water employed in the manufacture of pulp paper and water employed in cooling water systems, as well as other industrial waters, provide environments which are conducive to slime formation. The novel compositions of the present invention are mixtures which show unexpected synergistic activity against microorganisms, including bacteria, fungi and algae, which produce slime in aqueous systems. The slime, of course, is objectionable from an operational and/or an aesthetic point of view. Specifically, the invention is directed to and the use of composition comprising a combination of 5-chloro-4-phenyl-1,2dithiole-3-one and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1dioxide, or the derivatives of each. The inventive compositions inhibit the growth of slime in water, or more specifically, possess biocidal activity against bacteria, fungi and/or algae. The derivatives contemplated for use in accordance with the present invention are those which possess the capacity to kill or inhibit the growth of slime-forming microorganisms such as bacteria, fungi and algae.

Unite States Patent [191 Brink, Jr. et al.

[ DIOXIDE SLIME CONTROL COMPOSITION AND ITS USE [75] Inventors: Robert H. Brink, Jr., Doylestown;

Bernard F. Shema, Glenside; Roger L. Justice, Cornwells Heights, all of Pa.

[73] Assignee: Betz Laboratories, Inc., Trevose, Pa.

[22] Filed: Sept. 20, 1971 [21] Appl. No.: 182,258

Bnack r. 424/277 Primary Examiner-James 0. Thomas, Jr. Attorney, Agent, or Firm-Alexander D. Ricci [57] ABSTRACT The present invention relates to certain processes and 1 Jan. 21, 1975 compositions useful for inhibiting and/or controlling the growth of slime in water and, in particular, water employed for industrial purposes. Water employed in the manufacture of pulp paper and water employed in cooling water systems, as well as other industrial waters, provide environments which are conducive to slime formation. The novel compositions of the present invention are mixtures which show unexpected synergistic activity against microorganisms, including bacteria, fungi and algae, which produce slime in aqueous systems. The slime, of course, is objectionable from an operational and/or an aesthetic point of view. Specifically, the invention is directed to and the use of composition comprising a combination of 5- chloro-4-phenyl-1,2-dithiole-3-one and 3,3,4,4- tetrachlorotetrahydrothiophene-1,l-dioxide, or the derivatives of each. The inventive compositions inhibit the growth of slime in water, or more specifically, possess biocidal activity against bacteria, fungi and/or algae. The derivatives contemplated for use in accordance with the present invention are those which possess the capacity to kill or inhibit the growth of slimeforming microorganisms such as bacteria, fungi and algae.

10 Claims, N0 Drawings DIOXIDE SLIME CONTROL COMPOSITION AND ITS USE BACKGROUND OF THE INVENTION The formation of slime by microorganisms is a problem which attends many systems. For example, lagoons, lakes, ponds, pools and such systems as cooling water systems and pulp and paper mill systems all pos' sess conditions which are conducive to the growth and reproduction of slime-forming microorganisms. In both once-through and recirculating cooling systems, for example, which employ large quantitites of water as a cooling medium, the formation of slime by microorganisms is an extensive and constant problem.

Airborne organisms are readily entrained in the water fromcooling towers and find this warm medium an ideal environment for growth and multiplication. Aerobic and heliotropic organisms flourish on the tower proper while other organisms colonize and grow in such areas as the tower sump and the piping and passages of the cooling system. Such slime serves to deteriorate the tower structure in the case of wooden towers. In addition, the depositioon of slime on metal surfaces promotes corrosion. Furthermore, slime carried through the cooling system plugs and fouls lines, valves, strainers, etc. and deposits on heat exchange surfaces. In the latter case, the impedance of heat transfer can greatly reduce the efficiency of the cooling sysem.

In pulpand paper mill systems, slime formed by microorganisms is also frequently and, in fact, commonly encountered. Fouling or plugging by slime also occurs in the case of pulp and paper mill systems. Of greater significance, the slime becomes entrained in the paper produced to cafise breakouts on the paper machines with consequent work stoppages and the loss of production time or unsigntly blemishes in the final product; this, of course, results in rejects and wasted output. The previously discussed problems have resulted in the extensive utilization of biocides in cooling water and pulp and paper mill systems. Materials which have enjoyed widespread use in such applications include chlo rine, organo-mercurials, chlorinated phenols, organobromines, and various organo-sulfur compounds. All of these compounds are generally useful for this purpose but each is attended by a variety of impediments. For example, chlorination is limited both by its specific toxicity for slime-forming organisms at economic levels and by the ability of chlorine to react which results in the expenditure of the chlorine before its full biocidal function may be achieved. Other biocides are attended by high costs, odor problems and hazards in respect to storage, use or handling which limit their utility. To date, no one compound or type of compound has achieved a clearly established predominance in respect to the applications discussed. Likewise, lagoons, ponds, lakes and even pools, either used for pleasure purposes or used for industrial purposes for the disposal and storage of industrial wastes become, during the warm weather, besieged by slime due to microorganism growth and reproduction. In the case of the recreational areas, the problem of infection, odor, etc. is obvious. In the case of industrial storage or disposal of industrial materials, the microorganisms cause additional problems which must be eliminated prior to the materials use or the waste is treated for disposal.

It is the object of the present invention to provide compositions for controlling slime-forming microorganisms in aqueous systems, such as cooling water systems and pulp and paper mill systems, and for controlling slime formation or microorganism populations in aqueous bodies in general. Moreover, another object of the invention is the provision of methods for preserving materials and for controlling slime-forming microorganisms in any aqueous system which is conducive to the growth and reproduction of microorganisms and, in particular, cooling water and paper and pulp mill systems. These methods employ a combination of 5- chloro-4-phenyl-1,2-dithiole-3-one and 3,3,4,4- tetrachlorotetrahydrothiophene-1,l-dioxide, or derivatives of each. The derivatives must possess the property of being biocidally active against bacteria, fungi and/or algae, i.e., either kill or inhibit the growth of these microorganisms.

In the practice of the invention, the combination is added to the particular material to be preserved or to the system being treated, for example cooling water systems, paper and pulp mill systems, pools, ponds, lagoons, lakes, etc., in a'quantity adequate to control the slime-forming microorganisms which are contained by, or which may become enterained in, the system which is treated. It has been found that such compositions and methods control and growth and occurrence of such microorganisms as may populate these particular sytems.

GENERAL DESCRIPTION OF THE INVENTION dithiole-B-one compound and from about 5 to about of 3,3,4,4-tetrachlorotetrahydrothiophene-1,I-

dioxide. When these two ingredients are mixed either beforehand or by addition to the aqueous system individually, the resulting mixtures possess ahigh degree of slimicidal activity which could not have been predicted beforehand from the known activity of the individual ingredients comprising the mixture. Accordingly, it is therefore possible to produce a more effective slimecontrol agent than has previously been available. Because of the enhanced activity ofthe mixture, the total quantity of biocide required for an effective treatment may be reduced. In addition, the high degree of biocidal effectiveness which is provided by each of the ingredients may be exploited without use of the higher concentrations of each. This feature is not only important and advantageous from an economical point of view, but also most desirable from the pollution or ecological standpoints. In this regard, it might be pointed out that the smaller the amount of a chemical that is required for effective treatment, the smaller the problem in treating the wastes from these systems. In both cooling water systems and in paper and pulp mill systems, certain discharge of waste water, e.g., blowdown in cooling water systems, is a necessity. However, because of the current concern and legislation regarding the discharge of wastes, the effluent waste water must be treated to reduce and, hopefully, to eliminate any undesirable constituents. This treatment, .of course, is time-consuming and costly. Accordingly, a reduction in additive usage will result in a corresponding reduction in costs for the treatment of wastes containing these additives.

To demonstrate the synergism which is obtainable from the combination 3,3,4,4- tetrachlorotetrahydrothiophenel,I-dioxide (supplied by Diamond Shamrock as D5 649) with the 5-chloro-4- phenyl-l,2-dithiole-3-one (supplied by Hercules Corporation under designation 8-1612), various tests were utilized and will be described following.

SPECIFIC EM BODIMENTS EXAMPLE 1 SYNERGISTIC COMBINATION:

Compound A: 5-chloro-4-phenyl-1,2-dithiole-3-one Compound B: 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide The compositions of this Example contained 5- chloro-4-phenyl-l,Z-dithiole-3-one (referred to as Compound A in the Test Equations and in Tables 1 through 1C) and 3,3,4,4-tetrachlorotetrahydrothiophene-1,l-dioxide (referred to as Compound B in this Example and in the Test Equations and in Tables 1 through 1C) in the weight ratios expressed in the Tables which follow. The compositions were tested for synergistic activity in accordance with the method described. The synergism test was utilized to evaluate each of the combinations of this Example. Synergistic Index Test Synergistic activity was demonstrated by adding Compound A and Compound B in varying ratios and over a range of concentrations to liquid nutrient medium which was subsequently inoculated with a standard volume of suspension of the bacterium Aerobacter aerogenes. Following two days incubation, the lowest concentration of each ratio which prevented growth of the bacteria was taken as the end point. Growth or nogrowth was determined by turbidity or clarity respectively in the medium. End points for the various mixtures were then compared with end points for the pure active ingredients working alone in concomitantly prepared culture bottles. Synergism was determined by the method described by Kull et al [F. C. Kull, P. C. Eisman, H. D. SYlwestrowicz and R. L. Mayer, Applied Microbiology, 9, 538-41, (1961)] and the relationships,

0.1/0 QB/Q. 1 is additivity 1 is antagonism l is synergism where,

Q, Quantity of Compound A acting alone, producing an end point Q Quantity of Compound 8 acting alone, producing an end point Q,, Quantity of Compound A, in the mixture, producing an end point Q, Quantity of Compound B, in the mixture, producing an end point For mixtures of Compounds A and B, and for Compound A and Compound B acting alone, the following results were observed:

It is evident from the data recorded in Table 1 that compositions of the present invention function to control slime growth due to microorganisms not only at equal portions of the respective ingredients, but also where just minor amounts of one or the other are present. This discovery of synergism at the lower levels is extremely valuable since it illustrates conclusively that the ingredients are synergistically compatible over the wide percentage by weight range.

BACTERICIDAL EFFECTIVENESS The bactericidal effectiveness of the mixture of Compound A and Compound B of this Example is demonstrated by the following Table in which the inhibiting power of a 50/50 by weight mixture of A and B is shown. Aerobacter aerogenes was employed as the test organism and a substrate technique was utilized. Specifically, the biocidal mixture was added in gradually increasing quantities to nutrient agar media which was then inoculated with A. aerogenes. The preparation was then incubated for 48 hours. The values set forth in the Table indicate the quantity of biocide required, in parts by weight for each one million parts by weight of the medium, in order to achieve complete inhibition of the growth of the test organism.

TABLE 1A Quantity (ppm) required for inhibition Biocidal Material of A. aemgenes FUNGICIDAL EFFECTIVENESS In order to test the effectiveness of the inventive mixtures in respect to fungi, evaluations were made following the procedures described by B. F. Shema and J. H. Conkey [Journal for the Technical Association of The Pulp and Paper Industry, 36, 2OA--30A, (1953)]. The described procedure generally entails incorporating the biocide under test in a nutrient substrate such as agar, malt, etc. and pouring the resulting medium into a Petri dish and allowing the medium to solidify. A button of fungus inoculum is placed on the surface of the solidified medium and the medium is incubated for a period of 14 days. After the period, the diameter of the colony is measured and compared with the diameter of the button of inoculum'originally placed upon the surface. If there is no increase in the diameter, the growth of the fungus is considered to be completely inhibited and the Aspergillus niger. 5

TABLE 1B vides a most desirable cost performance index, but also provides most desirable advantages from the aspects of I pollution abatement, waste treatment costs. and the preservation of the ecological strain. When the inventive compositions are employed in Quantity (ppm) for inhibition Biocidal Material Compound A (5%). Compound B (5%), lnert (90%) 90 SLlME CONTROL EFFECTIVENESS tem which was currently experiencing problems in respect to the formation of slime by microorganisms. Such tests do not demonstrate the efficiency of the biocide employed with respect to specific species of microorganisms but instead supply a practical demonstration of the efficacy of the biocide tested in relation to those communities of microorganisms which have evidenced their ability to form slime in actual industrial systems.

In the testing of recirculating water samples, a substrate evaluation was employed. In such testing identical portions of water samples are treated with varying concentrations of biocide and two portions are left untreated to serve as controls. The control portions are plated for total count at the beginning of biocidal treatment and all portions are plated for total count at some suitable time period(s) after beginning biocide treatment. Using the counts from the plating, the percentage kill (based on the initial control count) may be calculated. In this evaluation the water sample was taken from a white water system in a paper mill located in the northeastern United States. 1

commercial biocides, Pentachlorophenol and a Com- 45 mercial Product.

P. expansum A. niger the treatment of cooling or paper mill water, they are preferably utilized in the form of relatively dilute solutions or dispersions. For example, a preferred solution comprises between 5 to by weight of the synergistic combination in admixture with various solvents and solubilizing agents. An example of such a synergistic biocidal product comprises from about 5 to 10% by weight of 3,3,4,4-tetrachlorotetrahydrothiophere-1,1- dioxide from about 5 to 10% by weight of 5-chloro-4- phenyl-1,2-dithiole-3-one and the remainder composed of such materials as surfactants, stabilizers, organic solvents, such as alkanols, aromatic hydrocarbons and/or water.

Surfactants such as the alkylaryl polyether alcohols, polyether alcohols, sulfonates and sulfates, and the like, may be employed to enhance the dispersibility and stability of these dispersions. The foregoing solutions of the biocidal compositions are utilized in order to insure the rapid and uniform dispersibility of the biocides within the industrial water which is treated. It has been found that either aqueous or non-aqueous solvents are generally suitable in thepreparation of compositions of the invention, e.g., methyl cellosolve, organic solvents such as the aliphatic and aromatic hydrocarbons, e.g., kerosene. Based upon the synergism study as outlined above, it was ascertained that in the treatment of paper mill and cooling water, effective biocidal action is obtained when the concentration or treatment level of the combination of admixture of biocides is between 0.5 parts per million to 1000 parts per million, and preferably between 1 and 100 parts per million, based upon the total content of the aqueous system treated, such as the total quantity of cooling water or paper mill water.

TABLE 1C Quantity of Percent kill Biocidal Material biocide (ppm) after 3 hours Compound A (5%). Compound B (5%). lnert 10 28 do. 25 43 do. 50 67 do. I00 94 Pentachlorophenol 10 v 3 do. 25 4 do. 50 26 do. 100 99 Commercial Product (30% active: Combination of dithiocarbamates) l0 0 do. 25 11 do. 50 28 do. 100 89 A perusal of the recorded percentages clearly establishes that the composition of the present invention, al-

The compositions may also be utilized for the preservation of slurries and emulsions containing carbohythough less concentrated with respect to active ingredi- 5 drates, proteins, fats, oils, etc; dosage levels for this ents as compared to the two commercial products, gave excellent rates of kill even at low temperature levels. As earlier expressed, excellent performance of a biocidal composition at low treatment levels not only propurpose range in the vicinity of 0.01 to 5%. The compositions of the invention which can be prepared by merely combining the respective ingredients and mixing thoroughly at standard conditions may be fed continuously to the treated system, e.g., by means of a metered pump, or may be fed periodically at predetermined intervals calculated to control the growth of slime-forming organisms in the system. Naturally, in the treatment of cooling water, the feeding of the inventive compositions must be designed to compensate for blowdown in those systems which employ that expedient.

Although the foregoing has been specifically directed to liquid formulations, the combinations of the invention may, of course, be formulated dry with well-known pelletizing agents, e.g., sodium chloride, talc, aluminate, etc. to produce solid pellets or briquettes which are added directly to the systems to be treated. The pellets or briquettes, of course, dissolve in accordance with predetermined conditions or rates.

In describing the inventive subject matter, the expression composition has been utilized. However, it is to be understood that physical compositions or combinations are not the sole utility of the invention. If, for example, the separate ingredients of the composition" are added independently to a particular system, it is intended that this usage of the subject matter is within the scope of the invention and is to be construed within the broad interpretation of composition and/or combination.

As would be expected, the inventive composition may be added to the cooling water or paper and pulp mill systems at any convenient point. Naturally, in once-through or non-circulating system, the composition must be added upstream from the point or points at which microorganism control is desired. In circulating systems or pulp and paper systems, the compositions must be added at any point provided that the time lapse and the conditions experienced between point of addition and the point at which the effect of the composition is to be experienced are not so drastic as to result in the neutralization of the effect of the composition.

Although the invention has been described specifically as being directed to specific compositions comprising -chloro-4-phenyl-1,2-dithiole-3-one in combination with 3,3,4,4-tetrachlorotetrahydrothiophenel,l-dioxide, as described in Example 1, it is obvious that homologs, analogs, etc. of the respective compounds are operable for the purpose. The provision, of course, is that the derivatives possess biocidal or growth inhibitory capacities with respect to bacteria, fungi, and algae.

It should be noted that while the evidence has been derived from the treatment of samples taken from a paper and pulp mill aqueous system, the compositions and methods of the present invention are broadly applicable to the treatment of aesthetic waters as well as industrial waters such as cooling waters, waste water, streams, lagoons, etc. which are plagued by slimeforming organisms.

Having thus described the invention, what we claim l. A method for controlling the growth of the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found which comprises adding to said system so as to contact said microorganism an effective amount of a combination comprising 5-chloro-4-phenyl-l,2-dithiole-3-one and 3,3, 1,4- tetrachlorotetrahydrothiophene-l,2-dioxide and mixtures thereof, wherein the weight ratio of the dithiole to the 3,3,4,4-tetrachlorotetrahydrothiophene-l l dioxide is from about 5 to to about 95 to 5%.

2. A method according to claim 1 wherein the combination contains approximately 50%by weight of each of said dithiole-3-one and said compound.

3. A method according to claim 1 wherein the combination is added to said system in any amount of from about 0.5 to about 1000 parts by weight of said composition per parts by weight of said system.

4. A method according to claim 3 wherein the composition is added to said system in an amount of l to parts per million parts of said aqueous system.

5. A method according to claim 3 wherein the aqueous system is the aqueous system of a cooling water system.

6. A method according to claim 3 wherein the system is the aqueous system of a pulp and paper mill system.

7. A method of preserving materials which are subject to attack by the microorganism Aerobacter aerogenes which comprises incorporating in said material containing an amount of said microorganism from about 0.5 to 5% by weight of a combination comprising 5-chloro-4-phenyl-1,2-dithiole-3-one and 3,3,4,4- tetrachlorotetrahydrothiophene-l l dioxide and mixtures thereof, wherein the weight ratio of the dithiole to the dioxide is from about 5 to 95% to about 95 to 5%.

8. A composition which is effective in controlling the growth of the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found comprising 5-chloro-4-phenyl-1,2-dithiole-3-one and 3 ,3 ,4,4-tetrachlorotetrahydrothiophene-l l dioxide and mixtures thereof, wherein the weight ratio of the dithiole to the dioxide is from about 5 to 95% to about 95 to 5%.

9. A composition according to claim 8 wherein the composition contains approximately 50% by weight of each of said dithiole3-one and said compound.

10. A biocidal product which is effective in controlling the growth of the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found comprising from about 5 to 10% by weight of 5-chloro-4-phenyl-l ,2-dithiole-3-one and from about 5 to 1 0% by weight of 3,3,4,4- tetrachlorotetrahydrothiophene-l,l-dioxide and mixtures thereof, and the remainder composed of a material selected from the group consisting of surfactants, stabilizers, organic and inorganic solvents and mixtures thereof. 

2. A method according to claim 1 wherein the combination contains approximately 50% by weight of each of said dithiole-3-one and said compound.
 3. A method according to claim 1 wherein the combination is added to said system in any amount of from about 0.5 to about 1000 parts by weight of said composition per parts by weight of said system.
 4. A method according to claim 3 wherein the composition is added to said system in an amount of 1 to 100 parts per million parts of said aqueous system.
 5. A method according to claim 3 wherein the aqueous system is the aqueous system of a cooling water system.
 6. A method according to claim 3 wherein the system is the aqueous system of a pulp and paper mill system.
 7. A method of preserving materials which are subject to attack by the microorganism Aerobacter aerogenes which comprises incorporating in said material containing an amount of said microorganism from about 0.5 to 5% by weight of a combination comprising 5-chloro-4-phenyl-1,2-dithiole-3-one and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixtures thereof, wherein the weight ratio of the dithiole to the dioxide is from about 5 to 95% to about 95 to 5%.
 8. A composition which is effective in controlling the growth of the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found comprising 5-chloro-4-phenyl-1, 2-dithiole-3-one and 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixtures thereof, wherein the weight ratio of the dithiole to the dioxide is from about 5 to 95% to about 95 to 5%.
 9. A composition according to claim 8 wherein the composition contains approximately 50% by weight of each of said dithiole-3-one and said compound.
 10. A biocidal product which is effective in controlling the growth of the microorganism Aerobacter aerogenes in an aqueous system in which said microorganism is found comprising from about 5 to 10% by weight of 5-chloro-4-phenyl-1,2-dithiole-3-one and from about 5 to 10% by weight of 3,3,4,4-tetrachlorotetrahydrothiophene-1,1-dioxide and mixtures thereof, and the remainder composed of a material selected from the group consisting of surfactants, stabilizers, organic and inorganic solvents and mixtures thereof. 